Apparatus for cleaning and coating capillary tubes useful in gas chromatography

ABSTRACT

An integral system contained in a suitable housing which includes means for coating particulate support material with stationary phase chemicals, means for draining liquid from the coated support material, means for drying the coated support material, and means for transferring the dried, coated support material into a gas-chromatography column. Means for cleaning and coating capillary tubes is also disclosed. Additionally means for conditioning packed columns and capillary tubes is disclosed.

This is a division of application Ser. No. 681,604 filed Apr. 29, 1976,now U.S. Pat. No. 4,086,051, which in turn is a continuation ofapplication Ser. No. 495,500 filed Aug. 7, 1974, now abandoned, which inturn is a division of application Ser. No. 232,583, filed Mar. 7, 1972,now U.S. Pat. No. 3,831,555.

BACKGROUND OF INVENTION

In the art of gas-liquid chromatography (GLC), it is necessary toprepare packed columns as well as coated capillary tubes which areemployed in conjunction with a suitable detector instrument, gaschromatograph, for obtaining analytical data relative to chemicalcompositions of a highly complex organic substance e.g., essential oils,perfumes, flavors, etc. The preparation of a packed column involvesfirstly, coating a suitable particulate packing support with a layer ofstationary phase chemical, drying the coated support, and thentransferring the coated and dried packing into a column of desireddimension in a manner such that the packing material is uniformly orhomogeneously distributed throughout the column. The preparation ofcapillary tubes involves firstly, cleaning a tube with various solutionsand then coating the walls thereof with a layer of stationary phasechemical.

In the case of gas-solid chromatography (GSC), the wide bore columns ofdesired dimension are packed with an inert solid support, such as,Chromosorb porous polymer beads.

Various packing supports and stationary phase chemicals are well knownin the gas chromatography art. Typical packing supports include inertmaterials such as diatomaceous earths, glass beads, polymer beads,crushed fire brick and the like. Stationary phase chemicals includepolyesters, polyethylene glycols, methyl and phenyl silicones,substituted silicones as well as many other chemicals.

Various techniques and devices are known in the prior art for performingindividual steps involved in the preparation of columns and capillarytubes. For example, U.S. Pat. No. 3,513,562 describes a fluidized dryingdevice for drying coated packing support materials. The use of capillarytubes coated with stationary phase materials is described in U.S. Pat.No. 2,900,478. Vibrating devices, for example, are known for the purposeof assisting in the uniform packing of gas chromatography (GC) columns.While the various prior methods and means are operable to produce packedcolumns and capillary tubes which may perform adequately for manyapplications, there has remained a need to maximize efficiency of theentire procedure for preparation of columns and capillary tubes suchthat the time and expense of preparing such means for use in gas-solidand gas-liquid chromatographic analyses might be substantially reduced.There has also remained prior to this invention a need for preparingpacked columns with a very large number of theoretical plates andcapillary tubes which will yield more highly consistent and reproducibleanalytical results.

It is important to properly condition the packed and capillary columnsbefore using them for analysis of the complex mixture of organiccompounds. In the prior art, while conditioning the columns, one end ofthe column is connected to the inlet of the carrier gas whereas theother end is left open to the atmosphere by not connecting it to thedetector inlet which otherwise would contaminate the detector system.Thus, in order to meet the aforementioned pre-requisite, very expensiveand highly sophisticated gas-chromatograph units are employed therebyincreasing the time and expense of preparing such columns forsatisfactory use in gas-solid and gas-liquid chromatography. Hence,there has been a great need for a column pre-conditioning means thatwould be more efficient, and economical to achieve this desired end.

BRIEF DESCRIPTION OF THE INVENTION

In accordance with the present invention a system is provided which isuseful for the coating of the particulate support material withstationary phase chemicals, drying or preconditioning the coated supportand transferring the prepared coated support material into the GC columnin an efficient and highly satisfactory manner. The integrated means ofthe present invention is also useful for cleaning and coating ofcapillary tubes employed in GLC analysis as well as in packing thecolumns with porous polymer solid supports such as Chromosorb polymerbeads used in gas-solid chromatography.

The system comprises the following basic and essential elements.Firstly, a housing means is provided to maintain the means hereinafterrecited. The housing means will usually include a suitable face panelupon which the various valves, gauges, power switches, pyrometer andflow meters can be placed. The various conduit means, pumps, heater, andother operating parts will preferably be enclosed within the housing.

A first port means is provided which is connected to an extrinsiccoating and drying column or to a reservoir for cleaning and coatingcapillary tubes. The port means are preferably located in the side panelwalls of the housing means and the various extrinsic columns, tubes,flasks, etc. are removably connected to the ports but located outside ofthe housing. Vacuum means such as a conventional vacuum pump ispreferably provided in the housing for effecting the various draining,evacuating and transferring operations performed in the preparation ofgas chromatography columns and capillary tubes. The vacuum meanscommunicates with the port means through suitable conduit means.

Preferably, the vacuum means is connected to the port through anextrinsic trap flask which can be readily emptied and which is useful intrapping relatively expensive stationary phase chemicals when drainingexcess solution from a solid support coating operation.

A second port means communicates with the first port means through afirst conduit means which is equipped with flow control valves andheating means. When a source of inert gas, e.g., nitrogen gas cylinder,is connected to the second port means, the gas can be passed at adesired temperature and flow rate into the base of a suitable column todry coated packing or, alternatively, in a stripped-down embodiment ofthe system of the invention can be connected to a vessel employed forcleaning or coating capillary tubes to force solutions through suchcapillary tubes.

A second conduit means connected to an extrinsic packing column throughthird port means communicates with the nitrogen supply port to providemeans for transferring coated packing material from the packing columninto the gas-chromatography column to be packed.

The above-stated combination of means are capable of effecting thecoating, drying packing of wide-bore columns as well as cleaning andcoating of capillary tubes in accordance with the system of the presentinvention. However, the preferred and enlarged system of the presentinvention is hereinafter described.

It is apparent that the entire preparation of gas-chromatography columnsand capillary tubes can be effected in accordance with the presentinvention with maximum efficiency and minimum handling time. Minimizinghandling of support material during the coating and drying operationresults in more reproducible, evenly coated and efficient coatedsupports. In line with this invention very fine particles are readilyeliminated and the particular size of the final coated product made morehomogeneous. Overall, the columns prepared in accordance with thepresent invention are found to be superior in analytical performance tocolumns prepared by prior art methods.

The system of the present invention can also be employed to control thegas supply to a column conditioning unit, and is particularly useful inconjunction with the new column conditioning means hereinafterdescribed.

REFERENCE TO THE DRAWINGS

FIG. 1 of the drawings illustrates diagrammatically, in elevation, onepreferred embodiment of the system of the present invention.

FIG. 2 illustrates a novel and preferred column reservoir useful inpreparation of coated packing supports.

FIG. 3 illustrates a novel and preferred column reservoir useful inpacking gas chromatography columns.

FIG. 4 illustrates diagrammatically, in elevation, novel means usefulfor cleaning capillary tubes in conjunction with the system of thepresent invention.

FIG. 5 illustrates diagrammatically, in elevation, novel means usefulfor conditioning the packed columns and coated capillary tubes prior tousing them in a conventional gas chromatography instrument.

DETAILED DESCRIPTION OF INVENTION

The invention is hereinafter described in detail with reference made toFIGS. 1 thru 5 of the drawings. Housing 20 which can be made of metal,wood or plastic forms a container for the system hereinafter described.For example, a housing 30-inches high, 24-inches wide and 10-inches deepis suitable.

Port 1 serves as an inlet for nitrogen or other inert gas to conduit 2.Port 1 is preferably situated flush with the left side panel of housing20. Conduit 2 is made of any suitable metal, plastic or ceramicmaterial. For example, copper tubing 1/8-inch in diameter issatisfactory for all conduits. Valve 5F is provided in conduit 2 tocontrol the flow of inert gas which, for example, can be provided by anitrogen cylinder. The control knob of valve 5 is preferably situated onthe front panel surface of housing 20. Each item designated in thedrawing by "F" following the numeral is, likewise, situated on the frontpanel surface of housing 20. The ports such as 1, 118, 123, 436 and 78are preferably situated flush with the left side panel of housing 20while ports 142, 43 and 58 are flush with the right side panel.

Nitrogen purifier 11, which is preferably equipped with replaceablecartridges, serves to eliminate moisture and oil from commercial gradenitrogen.

Union cross 15 joins conduit 2 to conduits 14, 471 and 3. Auxillaryvalve 19F is provided in conduit 3 to control the gas supply when dryingcoated support materials or when cleaning or coating capillary tubes.Auxillary valve 470 F in conduit 471 controls the gas supply to port 436which can be connected to the conditioning means, e.g. as shown in FIG.5.

Pressure gauge 152F is provided in conduit 3. This is intended primarilyfor use when coating and drying solid supports and packing wide-borecolumns and is preferably a 0-200 psi gauge. This gauge can also be usedfor cleaning or coating capillary tubes up to 200 psi. Gauge 152F shouldbe isolated from the high pressure system to prevent damage thereto byclosing valves 134F and 19F when 152F is not in use. Union cross 27renders conduit 4 in open communication with conduits 3 and 72.

Conduit 14 communicating between union cross 15 and port 142 is providedchiefly for use in cleaning capillary tubes when the pressure which isrequired exceeds about 200 psi. This line may be isolated where suchcleaning operation is not performed or eliminated by modification ofgauge 152F. Control valve 307F is situated in conduit 14. Pressure gauge151F is preferably graduated 0-400 psi. Conduit 14 communicates withconduit 3 thru tee 138. Tee 300 and valve 301F are provided foremergency pressure release when employing elevated pressures in conduit14 for cleaning or coating capillary tubes.

Conduit 4 and control valve 31F are provided to supply nitrogen gas,e.g., for drying coated solid supports. Heating means 34 is provided incombination with pyrometer 167F interconnected by a thermocouple line 35in order to provide nitrogen gas heated to the desired temperature.Preferred heating means comprises an electrically heated aluminum blockaround which a stainless steel conduit is wound. In order to improveheat transfer the section of conduit wound around the aluminum block canbe reduced in diameter, e.g., from 1/8-inch to about 0.02-inch. A switch(not shown) can be provided on the front panel to regulate thetemperature of 34.

Union cross 39 provides a junction point among conduits 4, 6, 10 and 7.Conduit 6 and port 43 are provided, e.g., for coating and drying supportmaterial; and also for transferring cleaning solutions into thereservoir 192. Conduit 7, valve 54F and port 58 are provided as drainand evacuation means. Conduit 10, valve 127F and port 123 are providedfor use in loading the pack tube 96 with coated support material.

Vacuum pump 70 which is connected to an electric power source and line 8which can be a heavy gauge flexible tubing or the like are preferablyprovided as part of the system for use in draining, loading, chargingreservoir 192 and evacuating operations. A switch (not shown) can beprovided on the front panel of the housing to actuate pump 70.

Conduit 12 which communicates between port 118 and gas-flow meter 122 isprovided, e.g., for use in conjunction with packing a gas-chromatographycolumn with Chromosorb polymer beads or with coated packing supportmaterial or for measuring the flow rate through the columns beingconditioned.

Conventional vibrator 221 is preferably attached to the side panel ofhousing 20 for use in packing a gas-chromatography column. A switch (notshown) can be provided on the front panel to actuate 221.

Adjustable clamps 116 and 119 can be provided attached to the top of thehousing 20 for the purpose of holding-in-place columns such as 50 and 96employed in the coating and packing procedures as hereinafter described.

FIG. 2 illustrates a reservoir assembly useful in coating and dryingsolid support materials. Glass tube 50, e.g., is heavy, borosilicateglass 24" high and 1" inside diameter. Female-threaded knurled aluminumring 182 fits snugly around tube 50 and male threaded knurled aluminumring 183 fits snugly around glass funnel 48. They are assembled byscrewing the threads of 183 into 182. The base of tube 50 then holdswasher 186 snugly in place which, in turn, holds a removable, porousdisc 187 made of sintered glass or any other suitable material firmlyagainst the lip of the glass funnel. Flexible hose 185 is connected tothe base of funnel 48 and valve 47, e.g., by means of screw clampsdisposed at each end thereof. Copper tubing 184 connects the reservoirassembly with port 43.

Coil 153 is a thin-walled stainless steel tubing (1/8" O.D.) coiled andthen flattened along the coil and adapted to be inserted into glass tube50 for use in drying the coated material. The upper end 153B is shapedas a hook to fit over the upper end of 50. The bottom part 153A extendsinto the bottom portion of tube 50. The function of this device ishereinafter described with reference to drying coated packing material.

FIG. 3, illustrates a novel and preferred reservoir assembly for use intransferring coated or uncoated packing support material into awide-bore gas chromatography column. Elongated tube 96 made of heavy,borosilicate glass or other suitable material rated to withstand apressure of 200 psig is fitted at each end with female-threaded knurledaluminum rings 93 and 97. Tube 96, e.g., is 18-inches high and 1-inchinside diameter. A circular plate 103 having an outside diameter suchthat it fits snugly into the base of tube 96 is rigidly connected toelbow 105. Plate 103 is machined to provide a plano-concave surfacewhich aids in preventing the coated support material transferred intotube 96 from being crushed and fragmented while packing GC-column 101.When male threaded aluminum ring 102 engages 97, plate 103 is heldsnugly in place and provides a base for the assembly.

Flat plate 90 having a bent tee 82 rigidly connected thereto is held inplace by engaging male-threaded knurled aluminum ring 92 with 93 thefemale threaded knurled aluminum ring.

FIG. 4 illustrates novel means useful, e.g., for cleaning and coatingcapillary tubes. Elongated thick-walled cylinder 192 capable ofwithstanding elevated pressures up to about 2,000 psi is adapted withthreaded ends 194 and 193. Conduit 205 having threads 203 and 204 cut ineach end thereof engages threads 193 at the bottom of the cylinder.Tee-shaped conduit 196 engages threads 194 at the top of the cylinderthrough threads 206. Dip tube 195 is removably secured to the top of 196at threads 198 by means of threads 206 cut in nut 199 which is rotatablymounted on dip tube 195. Protruberances 201 and 200 restrain axialmovement of nut 199 on 195. Threads 202 are provided at the top of 195for making further connections to auxiliary means. The operation of thisassembly is described with reference to procedure for cleaning andcoating capillary tubes. The dip tube 195 is designed to transfercorrosive cleaning liquids such as nitric and nitrous acids, ammoniumand sodium hydroxides, etc., into cylinder 192 with great care andwithout danger to the analyst or to objects in the laboratory workingarea. All fittings are designed to give pressure-tight operation atabout 1500 psi. Cylinder 192 is made of stainless steel. Although acylinder of 150 to 500 cc capacity can be used, a cylinder of about 300cc capacity is preferred for cleaning capillary tubes. For coatingcapillary tubes a cylinder with 10 to 100 cc capacity could be employed,but a cylinder with 50 cc capacity is most desirable for this purpose.

FIG. 5 illustrates novel means useful for conditioning the packed andcapillary columns. This device includes an oven that can be electricallyheated up to 500° C. and equipped with connections for suspending widebore packed columns and capillary columns simultaneously in the oven.Means are also provided to ascertain the packing density by measuringthe column back pressure at any chosen temperature during conditioningwhich should later enable the analyst to choose the optimum flowsettings on a conventional gas chromatograph without going through thetedious and time consuming procedure of flow rate calibration. Necessaryfittings for connecting packed columns of 1/8" to 1/2" diameter tubingsup to 50 feet in length and capillary columns up to 1000 feet in lengthto the gas supply and to the flow measurement devices are provided. Theoven chamber is so designed that columns of every conceivable shape suchas straight biwalled columns, hair pin or folded hair pin, pan cake,helical or randomly coiled to 10" in diameter used in the gaschromatographic analyses of complex organic mixtures can be accomodatedreadily. Housing 500 which is preferably made of metal forms a containerfor the system hereinafter described. For example, a thermally insulatedsteel housing 36" high, 24" wide and 12" deep is suitable from aneconomic point of view. This will accomodate four packed wide borecolumns and two capillary columns each up to 50 feet and 1000 feet inlength respectively.

Ports 540, 541, 542, 543, 544 and 545 serve as inlets for nitrogen orother inert gas to individual columns. Ports 501E, 502E, 503E, 504E,505E and 506E serve as the outlet fittings for the exit end of thecolumns.

All ports, 540 to 545 and 501-E to 506-E are preferably situated flushwith the left side and right side panels of the housing 500.

The conditioning unit is connected to the unit contained in housing 20by connecting port 586 at the terminal part of conduit 521 to port 436.Union cross 522 connects pressure gauge 560, inlet conduit 521, andconduits 519 and 516. Gauge 560 is preferably graduated 0-200 psi andpermits measurement of the gas inlet pressure.

Conduit 519 is in communication with conduit 539 through valve 501 andflow controller 514.

Conduit 539 supplies inert gas to individual ports 540 thru 543. Valves501, 502, 503 and 504 are provided to control the gas supply toindividual columns connected to the ports 540, 541, 542 and 543,respectively.

Tees 570 through 573 situated at the positions indicated in FIG. 5connect the respective valves to the column inlet ports and are also incommunication with the rotary valve 508 through the correspondingconduits 525, 526, 527, and 528. Rotary valve 508 is a conventionalrotary valve, e.g., as made by R. S. Crum Co., for connecting any one ofconduits 525 thru 530, to pressure gauge 510.

Conduit 516 is in communication with conduit 524 which supplies inertgas to capillary columns connected to the ports 544 and 545 through therespective valve 505 and 506. A pressure regulator e.g., 0 to 50 psi,with a gauge 509 and a control valve 507 is provided in conduit 524 toregulate the gas supply.

Tees 574 and 575 connecting respectively the valve 505 to port 544 and506 to 545 are in communication with the rotary valve 508 through therespective conduits 529 and 530.

Rotary valve, preferably a 7-way valve, is connected to a pressuregauge, e.g., 0-200 psi, and is in communication with the inlet of thecolumns through the conduits 525 through 530. Choosing the appropriatepositions by means of a knob on the rotary valve enables the analyst toread the back pressure at the inlet of the column which is beingconditioned. By placing the knob to the vent position, pressure on thegauge can be released.

Thermocouple lead 590 can be connected to pyrometer 167F within housing20 to read the temperature of the oven.

Column outlets, 501E, through 506E can be connected to the flow meter122F on the housing 20 through conduit 111 and port 118. This enablesthe analyst to determine the flow rate through the column.

PROCEDURE FOR COATING AND DRYING SOLID SUPPORT MATERIAL

Column reservoir 50 is assembled as described with reference to FIG. 2and is held in place by clamp means 119. Conduit 184 is connected toport 43. Coil 153 is removed during the coating procedure. All valvesincluding valve 47 should be closed. Any desired coating solution isintroduced through the open top into 50. A pre-weighed amount ofparticulate support material is then introduced into the coatingsolution and permitted to stand undisturbed for a suitable period oftime, e.g., 5-20 minutes.

The following procedure is followed only in the case of solution coatingtechnique but omitted when a slurry coating method is used.

The top of tube 50 is preferably closed off once solid support materialis added by inserting in the upper part thereof a vertically elongatedtube containing a special mixture of oxysorb, ascarite and activatedcharcoal. This eliminates oxygen moisture, and organic vapors from airentering the system while draining the excess solution.

Drain flask 62 is connected to port 58 and line 8. Vacuum pump 70 isstarted and valves 54F and 47 are opened to permit draining of solutionfrom tube 50.

When solution is removed from tube 50 leaving wet coated solid material,hose 185 is disconnected from valve 47. The same solvent used fordissolving the stationary phase chemical can be introduced into valve47, with the vacuum system on, in order to dissolve any stationary phasematerial, which may be very expensive. The dissolved material is thentrapped in flask 62 from which it can be recovered for reuse.

Once the solid support material in tube 50 has been coated, thefollowing procedure is observed to dry the coated support. Pump 70 isturned off and valve 54F is closed. Hose 185 is reconnected to valve 47and vertically elongated tube is removed from the top of 50. Coil 153which has been coated with oil or other sticky substance is insertedinto tube 50 such that 153A extends well below the surface of the coatedsupport material. Valves 31F and 19F are opened. Nitrogen supply isconnected to port 1 and the tank delivery gauge is set to 50-100 psi.Valve 5F is opened slowly until the pressure reading on 152F is, e.g.,between about 10-20 psi. The nitrogen gas flows thru purifier 11 andthru heater 34 for elevation in temperature to a desired level fordrying the support material in tube 50. Coil 153A prevents the wet cakeof coated support material from rising as a mass during the initialdrying period. Thereafter the flow of gas upwardly thru porous sintereddisc 187, which acts as a sparger or distributor, and the particulatesolids tends to fluidize the material in tube 50. The finer particlestend to migrate to the top of tube 50 due to elutriation by the inertgas are trapped on 153 and then discarded. Thus, the particulate supportmaterial is made more homogeneous relative to particle size distributionduring the drying step in tube 50.

When the support material in tube 50 is dried and free flowing, electricpower supply to the heater is turned off and all valves are closed toshut off the gas supply. Tube 50 is disconnected at valve 47 and thecoated support material is transferred to a suitable air-tight containerfor storage until the packing operation. Alternatively, it iscontemplated that tube 50 can be employed directly in place of thepacking reservoir 96, after assembling the appropriate parts describedwith reference to FIG. 3.

PROCEDURE FOR PACKING WIDE-BORE COLUMNS

The assembled packing column 96, described with reference to FIG. 3 isheld in place by clamp means 116. Line 85 is connected to tee 82 at 82A.The alternate opening 82B is connected to gas supply port 78 by means ofconnecting line 83. Port 123 is connected to elbow 105 at the base oftube 96 by means of conduit 115. Special connector 108 is packed withstainless steel or glass wool to prevent the coated packing materialfrom being drawn below that point. With all other valves closed, valves127F and 54F are opened while vacuum pump 70 is started and theprecoated and dried support material in the air-tight container 84 isheld at the end of line 85. This draws the coated packing supportmaterial from container 84 into tube 96.

Once the desired amount of support material whether coated or uncoatedhas been transferred into 96 the following procedure is employed to packwide-bore GC columns, e.g., 1/8-3/4-inch outer diameter GC columns withthe support material. Line 85 is disconnected from 82A and the openingis closed with a suitable plug. Line 115 is disconnected from 105.

The GC column 101 bent to the desired shape is brought into contact withvibrator 221. One end of this column is connected to 105, while theother end is connected to port 118 by means of conduit 111. Specialconnector 108 is used between the GC column end and the conduit 111. Thenitrogen supply is connected to port 1. By opening valves 5F and 19F thepressure reading on 152F is brought to about 100 psi, for example, whichis suitable for packing a column 10 ft. long and 1/8-inch outerdiameter. The vibrator 221 is turned on. With valves 134F and 31Fclosed, valve 74F is opened causing packing support material to flowfrom tube 96 into the GC column 101. When the column is packed in auniform manner the pressure on 152F and the flow reading on 122F becomeconstant and stable. If there is an obstruction in the tube the flowreading on 122F will fall to zero and the pressure shown on 152F will behigher than expected. It is apparent that columns of constant dimensionpacked with the same coated support material will exhibit the same finalflow reading on 122F and pressure on 152F. Thus, the system of thisinvention permits preparation of highly reproducible and reliable packedcolumns.

When the gas chromotography column is packed, the vibrator 221 andnitrogen valve 5F are turned off. When the pressure on 152F shows zerothe column may be disconnected, conditioned and then connected to aconventional GC detector.

PROCEDURE FOR CONDITIONING COLUMNS

The following procedure is followed to condition the packed columns orcoated capillary tubings.

In order to condition the columns or the capillary tubings, one endthereof, preferably, the detector end is connected to any of the inletports 540 through 543 for packed columns or 544-545 for the capillarytubings. The other end is connected to one of the exit ports 501-Ethrough 506-E. The oven temperature is set to about 20° C. below themaximum recommended temperature for that particular stationary phase,for example 100° C. The gas supply to the column is then started. Inorder to obtain an appropriate flow of gas the knob on rotary valve 508is set to the proper position to read the column inlet pressure on gauge510. The pressure reading on gauge 510 is then set to an appropriatereading at the proper selected temperature by adjustment of controlvalve 501, e.g., 40 psi for a 10 feet by 1/8" inches packed column.

The column is conditioned at the temperature chosen for a period ofabout 2 to 24 hours for packed columns and capillary tubings and perhapsfor several days depending upon the purity and homogenity of liquidstationary phase or the inert solid support, such as, chromosorb porouspolymer beads and also depending upon whether the columns so preparedare intended for GC-coupled MS-analyses. For example, the column isconditioned at 200° C. for 24 hours with gas flowing through the column.

During the column conditioning period the flow rate at the column exitat any column temperature can be conveniently measured by connecting thecolumn exit to the flow meter 122F through conduit 111 and port 118.Further measurement of the column back pressure at the carrier gas inletwhich bears a direct relationship to the flow through the column can bedetected by means of gauges 510 or 509.

After the specified period of time, e.g., 24 hours, the oven is cooledto room temperature and the column temperature is reset, e.g., to 100°C. and the pressure reading on gauge 510 is reset to 40 psi. The flowrate at the column exit is measured by connection with 122F. Forexample, the flow rate is 30 c.c. per minute at 100° C. and 40 psi inletpressure. The conditioned column can now be removed and transferred to aGC unit. If the inlet pressure is set to 40 psi at a column temperatureof 100° C., the flow rate of gas will automatically be 30 cc per minute.

Important features and advantages of the column conditioning unitinclude the following:

1. Allows the analyst to determine the desired optimum flow ratecalibration during the conditioning operation;

2. Abbrogrates contamination of components separated by gaschromatography thus more reliable and accurate spectroscopic data, e.g.,infra-red and mass spectroscopic data, can be obtained on GC purematerials;

3. Columns conditioned employing the unit described in the presentinvention ameliorates the results of temperature and flow programmed gaschromatographic analyses;

4. Saves the time of very expensive and highly sophisticated instrumentsthat are otherwise occupied for conditioning columns;

5. Eliminates base line drift during programmed GC-analyses thusimproving integration accuracy;

6. The unit can be used for simultaneous conditioning of packed as wellas capillary columns of every conceivable shape such as straight,coiled, hairpin, pancake, helical, etc.;

7. Individual column back pressure can be measured during columnconditioning by operating a selector valve switch. This not only enablesthe analyst later to choose the optimum flow settings on a conventionalgas chromatograph but also with minimum effort to check the similarityof two columns packed with the same uncoated or coated support;

8. Eliminates the contamination of detectors with the lower molecularweight fragments normally present in the stationary liquid phases thatwould clute off of the wide bore packed and wall coated capillarycolumns during conditioning. Constant deposition of such impurities onthe detector components would have an adverse effect upon thesensitivity of such detectors, viz., thermal conductivity, flameionization, electron capture and micro-cross section detectors.

COMPARATIVE ANALYTICAL DATA ON THE PERFORMANCE OF COLUMNS PREPAREDACCORDING TO THE PRESENT INVENTION AND THE KNOWN ART

    ______________________________________                                                 PRESENT INVENTION                                                                            KNOWN ART                                                      t'.sub.R                                                                            K        R       t'.sub.R                                                                           K     R                                  ______________________________________                                        alpha-pinene                                                                             16.25   54.0           8.75 42.5                                   beta-pinene                                                                              27.50   79.0     3.0   12.50                                                                              75.0  1.6                              myrcene    31.25   104.0    1.5   17.50                                                                              87.5  0.6                              limonene   43.75   145.8    3.3   22.50                                                                              112.5 1.3                              gamma-terpinene                                                                          55.00   183.3    3.6   28.75                                                                              139.5 1.5                              column length                                                                             3000 mm          3000 mm                                          column                                                                        diameter (OD)                                                                            3.125 mm         3.125 mm                                          theoretical                                                                   plates     91,800           27,880                                            HETP       0.032 mm         0.107 mm                                          ______________________________________                                         NOTE:                                                                         t'.sub.R = Adjusted retention distance (mm)                                   k = Partition ratio                                                           R = The resolution of two adjacent peaks                                      HETP = Height Equivalent to Theoretical Plates                           

PROCEDURE FOR CLEANING AND COATING CAPILLARY TUBES

The following procedure is employed for cleaning and coating capillarytubes, e.g., a stainless steel tubing having 0.0625-inch externaldiameter and 0.02-inch internal diameter and 250 feet long. It is highlyuseful in the GC-MS analysis of very complex mixtures of organiccompounds such as essential oils and flavors.

In order to clean the capillary tube, one end thereof is connected toconduit 205 and the other end of the capillary tube is closed with asuitable plug. The means shown in FIG. 4 is fully assembled with diptube 195 in place. Conduit 207 is connected at 202 and the other endthereof is dipped well below the cleaning fluid level in container 210.Spigot 197 is connected to vacuum source, e.g., by means of a suitableconnecting conduit communicating between 197 and port 43. Valve 54F isopened after the vacuum pump 70 is turned on and all other valves areclosed. When the desired amount of cleaning fluid has been transferredinto 192 the vacuum is shut off. Spigot 197 is disconnected from thevacuum conduit and plugged by suitable means. Dip-tube 195 preventscontact of the various surfaces of tee conduit 196 with highly corrosivecleaning fluids and, of course, make disassembly of the cylinder saferfor the analyst or technician.

After cleaning fluid has been transferred into 192, dip tube 195 isremoved from the top of tee conduit 196 by unscrewing nut 199. One endof conduit 212 is then connected to threads 198 and the other end isconnected to high pressure gas supply port 142. The plug employed toclose off the outlet end of the capillary column is removed and aftermaking sure all other valves are closed, valves 5F and 307F are opened.The pressure on gauge 151F is adjusted to the desired level dependingupon the length and internal diameter of the capillary tube, nature ofcleaning solution, etc., e.g., between 100-400 psi such that the flow ofnitrogen gas forces solution downwardly from cylinder 192 through thecapillary tube. To disrupt the operation at any instant close valve 307Fand open valve 301F. This procedure may be repeated as many times as isrequired to effect cleaning of the capillary tube.

Coating capillary tubes can be accomplished by the same procedure andmeans hereinabove described except that a suitable coating solution issubstituted for the cleaning solution. It is also preferred to employ asmaller cylinder, e.g., as represented by cylinder 220 shown in FIG. 1.While the larger cylinder 192 can be employed for cleaning the capillarytubes, a cylinder of the same design as described with reference to FIG.4 but having a volume of 10-100 cc is most desirable for performingcoating operation.

In the coating procedure a pressure of 50-110 psi, for example, asindicated on gauge 151F is preferred depending upon the physicalcharacteristics of the coating solution and dimensions of the tube to becoated. It is also desirable to continue the flow of nitrogen throughthe capillary tube at a pressure, e.g., 50 psi, for 12 to 24 hours afterthe desired quantity of coating solution has been passed through thecleaned capillary tube.

A procedure for dynamic coating of capillary tubes is described inDijkstra, G., and J. DeGoey, Gas Chromatography 1958, D. H. Desty,Editor, Butterworths, London, 1958, p, 56. According to this method asuitable stationary phase is dissolved in a solvent and then passedthrough the capillary tube. The deposition of stationary phase materialon the walls of the capillary tube is governed, among other factors, bythe rate of flow of solution through the tube, concentration ofstationary phase and other factors related to specific compositions.

The present invention provides means for eliminating physical variablesrelative to the coating procedure and thereby achieving morereproducible results as well as more efficient preparation of capillarytubes.

Having thus described the invention with reference to specificembodiments thereof many modifications and alterations thereof willbecome apparent to those skilled in the art without departing from thespirit and scope thereof.

I claim:
 1. A device useful for cleaning and coating capillary tubeswhich comprises: an elongated vessel having walls capable ofwithstanding elevated pressures up to about 2000 psi, an elongatedconduit having an inside open passageway removably inserted into one endof said elongated vessel so as to form a pressure-tight connectiontherewith, an elongated tube adapted with connection means at one endthereof removably fastened to the upper end of said elongated conduit soas to form a pressure tight connection therewith, said tube dependingthrough the open passageway inside of said conduit and extending intosaid elongated vessel, means for connecting the top portion of said tubeto auxiliary fluid lines, said elongated conduit being adapted withmeans situated on the side wall thereof for connection to a vacuum line,and means removably insertable into the alternate end of said elongatedvessel for forming a pressure tight connection with a capillary tube orthe like, wherein a capillary tube is removably inserted in said meansremovably insertable into the alternate end of said elongated vessel,and wherein a desired amount of cleaning fluid is drawn into said vesselfrom said elongated tube by connecting said vacuum line connecting meansto a vacuum source, and then said vessel is pressurized to flow thecleaning fluid out of the vessel into said capillary tube.
 2. The deviceof claim 1 wherein said capillary tube is stainless steel and has a0.0625 inch external diameter and 0.02 inch internal diameter.